Hydrogen bromide
Encyclopedia
Hydrogen bromide is the diatomic molecule H
Br
. HBr is a gas at standard conditions. Hydrobromic acid
forms upon dissolving HBr in water. Conversely, HBr can be liberated from hydrobromic acid solutions with the addition of a dehydration agent, but not by distillation
. Hydrogen bromide and hydrobromic acid are, therefore, not the same, but they are related. Commonly, chemists refer to hydrobromic acid as "HBr", and this usage, while understood by most chemists, is imprecise and can be confusing to the non-specialist.
) that boils at 126°C. Boiling less concentrated solutions releases H2O until the constant boiling mixture composition is reached.
HBr adds to alkenes to give bromoalkanes, an important family of organobromine compound
s:
HBr adds to alkynes to yield bromoalkenes. The stereochemistry
of this type of addition is usually anti:
HBr adds to the haloalkene to form a geminal
dihaloalkane. (This type of addition follows Markovnikov's rule
):
Also, HBr is used to open epoxides and lactones and in the synthesis of bromoacetals. Additionally, HBr catalyzes many organic reactions.
HBr has been proposed for use in a utility-scale flow-type battery.
and bromine
are combined at temperatures between 200-400 °C. The reaction is typically catalyzed by platinum
or asbestos
.
with phosphoric acid
or diluted sulfuric acid
:
Concentrated sulfuric acid is ineffective because HBr formed will be oxidized to bromine
gas:
The acid may be prepared by several other methods, as well, including reaction of bromine either with phosphorus
and water, or with sulfur
and water:
Alternatively, it can be prepared by the bromination of tetraline (1,2,3,4-tetrahydronaphthalene):
Alternatively bromine can be reduced with phosphorous acid:
Anhydrous hydrogen bromide can also be produced on a small scale by thermolysis of triphenylphosphonium bromide in refluxing xylene
.
HBr prepared by the above methods can be contaminated with Br2, which can be removed by passing the gas through Cu turnings or through phenol.
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
Br
Bromine
Bromine ") is a chemical element with the symbol Br, an atomic number of 35, and an atomic mass of 79.904. It is in the halogen element group. The element was isolated independently by two chemists, Carl Jacob Löwig and Antoine Jerome Balard, in 1825–1826...
. HBr is a gas at standard conditions. Hydrobromic acid
Hydrobromic acid
Hydrobromic acid is a strong acid formed by dissolving the diatomic molecule hydrogen bromide in water. "Constant boiling" hydrobromic acid is an aqueous solution that distills at 124.3 °C and contains 47.6% HBr by weight, which is 8.89 mol/L. Hydrobromic acid has a pKa of −9, making it a...
forms upon dissolving HBr in water. Conversely, HBr can be liberated from hydrobromic acid solutions with the addition of a dehydration agent, but not by distillation
Distillation
Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction....
. Hydrogen bromide and hydrobromic acid are, therefore, not the same, but they are related. Commonly, chemists refer to hydrobromic acid as "HBr", and this usage, while understood by most chemists, is imprecise and can be confusing to the non-specialist.
General description
At room temperature, HBr is a nonflammable gas with an acrid odor, fuming in moist air because of the formation of hydrobromic acid. HBr is very soluble in water, forming hydrobromic acid solution, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.38% HBr by weight form a constant-boiling mixture (reverse azeotropeAzeotrope
An azeotrope is a mixture of two or more liquids in such a ratio that its composition cannot be changed by simple distillation. This occurs because, when an azeotrope is boiled, the resulting vapor has the same ratio of constituents as the original mixture....
) that boils at 126°C. Boiling less concentrated solutions releases H2O until the constant boiling mixture composition is reached.
Uses of HBr
There are many uses of HBr in chemical synthesis. For example, HBr is used for the production of alkyl bromides from alcohols:-
- ROH + HBr → RBr + H2O
HBr adds to alkenes to give bromoalkanes, an important family of organobromine compound
Organobromine compound
Organobromine compounds are organic compounds that contain carbon bonded to bromine. The most pervasive is the naturally produced bromomethane. One prominent application is the use of polybrominated diphenyl ethers as fire-retardants. A variety of minor organobromine compounds are found in...
s:
-
- RCH=CH2 + HBr → RCH(Br)–CH3
HBr adds to alkynes to yield bromoalkenes. The stereochemistry
Stereochemistry
Stereochemistry, a subdiscipline of chemistry, involves the study of the relative spatial arrangement of atoms within molecules. An important branch of stereochemistry is the study of chiral molecules....
of this type of addition is usually anti:
- RC≡CH + HBr → RC(Br)=CH2
HBr adds to the haloalkene to form a geminal
Geminal
In chemistry, the term geminal refers to the relationship between two functional groups that are attached to the same atom...
dihaloalkane. (This type of addition follows Markovnikov's rule
Markovnikov's rule
In organic chemistry, Markovnikov's rule or Markownikoff's rule is an observation based on Zaitsev's rule. It was formulated by the Russian chemist Vladimir Vasilevich Markovnikov in 1870....
):
-
- RC(Br)=CH2 + HBr → RC(Br2)–CH3
Also, HBr is used to open epoxides and lactones and in the synthesis of bromoacetals. Additionally, HBr catalyzes many organic reactions.
HBr has been proposed for use in a utility-scale flow-type battery.
Industrial preparation
Hydrogen bromide (along with hydrobromic acid) is produced on a much smaller scale than the corresponding chlorides. In the primary industrial preparation, hydrogenHydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
and bromine
Bromine
Bromine ") is a chemical element with the symbol Br, an atomic number of 35, and an atomic mass of 79.904. It is in the halogen element group. The element was isolated independently by two chemists, Carl Jacob Löwig and Antoine Jerome Balard, in 1825–1826...
are combined at temperatures between 200-400 °C. The reaction is typically catalyzed by platinum
Platinum
Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...
or asbestos
Asbestos
Asbestos is a set of six naturally occurring silicate minerals used commercially for their desirable physical properties. They all have in common their eponymous, asbestiform habit: long, thin fibrous crystals...
.
Laboratory synthesis
HBr can be synthesized by a variety of methods. It may be prepared in the laboratory by distillation of a solution of sodium or potassium bromidePotassium bromide
Potassium bromide is a salt, widely used as an anticonvulsant and a sedative in the late 19th and early 20th centuries, with over-the-counter use extending to 1975 in the United States. Its action is due to the bromide ion...
with phosphoric acid
Phosphoric acid
Phosphoric acid, also known as orthophosphoric acid or phosphoric acid, is a mineral acid having the chemical formula H3PO4. Orthophosphoric acid molecules can combine with themselves to form a variety of compounds which are also referred to as phosphoric acids, but in a more general way...
or diluted sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...
:
- 2 KBr + H2SO4 → K2SO4 + HBr
Concentrated sulfuric acid is ineffective because HBr formed will be oxidized to bromine
Bromine
Bromine ") is a chemical element with the symbol Br, an atomic number of 35, and an atomic mass of 79.904. It is in the halogen element group. The element was isolated independently by two chemists, Carl Jacob Löwig and Antoine Jerome Balard, in 1825–1826...
gas:
- 2 HBr + H2SO4 → Br2 + SO2 + 2H2O
The acid may be prepared by several other methods, as well, including reaction of bromine either with phosphorus
Phosphorus
Phosphorus is the chemical element that has the symbol P and atomic number 15. A multivalent nonmetal of the nitrogen group, phosphorus as a mineral is almost always present in its maximally oxidized state, as inorganic phosphate rocks...
and water, or with sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
and water:
- 2 Br2 + S + 2 H2O → 4 HBr + SO2
Alternatively, it can be prepared by the bromination of tetraline (1,2,3,4-tetrahydronaphthalene):
- C10H12 + 4 Br2 → C10H8Br4 + 4 HBr
Alternatively bromine can be reduced with phosphorous acid:
- Br2 + H3PO3 + H2O → H3PO4 + 2 HBr
Anhydrous hydrogen bromide can also be produced on a small scale by thermolysis of triphenylphosphonium bromide in refluxing xylene
Xylene
Xylene encompasses three isomers of dimethylbenzene. The isomers are distinguished by the designations ortho- , meta- , and para- , which specify to which carbon atoms the two methyl groups are attached...
.
HBr prepared by the above methods can be contaminated with Br2, which can be removed by passing the gas through Cu turnings or through phenol.